Process for making transparent silica glass

ABSTRACT

A crucible formed from pulverized particles of fused quartz is fired and vacuum dried to remove all water and is thereafter placed on a heated graphite form or susceptor shaped to conform to the surface of said article and rapidly heated in an induction furnace to a high temperature, in the range of about 3000*F. to about 3150*F. The crucible is maintained at a temperature in such range in a vacuum or in a helium atmosphere for a period of at least one minute sufficient to obtain full density while avoiding substantial devitrification. The vacuum drying preferably provides the glass of the crucible with an infrared absorption beta OH factor below .01 at a wavelength of 3.5 microns. A unique apparatus is provided to carry out the process rapidly and efficiently without forming significant amounts of cristobalite and to cause gases trapped in the crucible to move radially outwardly. The process minimizes devitrification and can be employed for mass production of precision transparent amorphous quartz glass products having excellent resistance to thermal shock.

Loxley et a1.

[ PROCESS FOR MAKING TRANSPARENT SILICA GLASS [75] Inventors: Ted A. Loxley, Mentor; Walter G.

Barber, North Perry; Walter W. Combs, Mentor; John M. Webb, Chagrin Falls, all of Ohio [73] Assignee: Sherwood Refractories, Inc., East Cleveland, Ohio [22] Filed: May 24, 1973 [21] Appl. No.: 363,622

Related U.S. Application Data [63] Continuation-in-part of Ser. No. 135,140, April 19,

1971, abandoned.

[52] U.S. Cl 65/18, 65/30, 65/32, 65/DIG. 8, 264/65, 264/66 [51] Int. Cl C03g 23/20 [58] Field of Search 65/18, 32, 30, DIG. 8, 65/134; 264/57, 65, 66

[56] References Cited UNITED STATES PATENTS 2,038,627 4/1936 Badger 65/DIG. 8 2,511,216 6/1950 Miller 65/D1G. 8 2,612,727 10/1952 Hordberg. 2,799,912 7/1957 Gregor 264/66 X 3,010,839 11/1961 Drumheller et al 65/18 X 3,116,137 12/1963 Vasilos et a1. 65/18 X 3,149,946 9/1964 Elmer 65/32 3,196,193 7/1965 Davies et a1. 264/66 X 3,261,676 l/1963 Morelock 65/18 3,320,045 5/1967 Weiss et al 65/335 3,396,220 8/1968 Dewsiyap et al.. 264/65 3,460,926 8/1969 Weaver 65/18 3,486,870 12/1969 Ver Vaart et a1.... 65/32 3,565,345 2/1971 Moltzan 239/422 3,565,346 2/1971 Carrel 239/422 OTHER PUBLICATIONS Handbook of Glass Manufacture Vol. II Fay V. Tooley Ogden Pub. Co. New York 1961 Pages 187 199.

Primary ExaminerS. Leon Bashore Assistant Examiner-Frank W. Miga [57] ABSTRACT A crucible formed from pulverized particles of fused quartz is fired and vacuum dried to remove all water and is thereafter placed on a heated graphite form or susceptor shaped to conform to the surface of said article and rapidly heated in an induction furnace to a high temperature, in the range of about 3000F. to about 3150F. The crucible is maintained at a temperature in such range in a vacuum or in a helium atmosphere for a period of at least one minute sufficient to obtain full density while avoiding substantial devitrification. The vacuum drying preferably provides the glass of the crucible with an infrared absorption beta OH factor below .01 at a wavelength of 3.5 microns. A unique apparatus is provided to carry out the process rapidly and efficiently without forming significant amounts of cristobalite and to cause gases trapped in the crucible to move radially outwardly. The process minimizes devitrification and can be employed for mass production of precision transparent amorphous quartz glass products having excellent resistance to thermal shock.

22 Claims, 5 Drawing Figures mmauswzm 3.837. 825

SHEEY 1 OF 4 pmmgnsarzmu I sum aor 4 PROCESS FOR MAKING TRANSPARENT SILICA GLASS This application is a continuation-in-part of copending application Ser. No. 135,140, filed Apr. 19, 1971, now abandoned, the disclosure of which is incorporated herein by reference.

The present invention relates to a process and apparatus for making transparent amorphous silica glass from particles of fused silica and more particularly to the manufacture of sintered fused silica crucibles and other transparent precision silica glass products having high resistance to thermal shock. The process makes it possible to mass produce precision transparent amorphous quartz glass articles at low cost without expensive glass working procedures.

Heretofore, fused silica has been fabricated by glass working, slip casting or pressing techniques. Glass working methods involve heating the glass to a temperature, such as 3500F. or higher, to lower the viscosity to a point where the glass may be subjected to plastic deformation, as by rolling, pressing or drawing. Such glass working methods are used extensively in spite of high cost and the need for specialized equipment and skilled technicians for the production of any but the most simple shapes.

Slip casting has also been used extensively because it is the least expensive of all fabrication methods, does not require expensive equipment, and is able to handle complex shapes, but the standard slip casting methods known prior to the present invention were unsatisfactory for making precision high quality fused quartz products such as transparent quartz glass articles. In some instances, the surface of the slip-cast fused silica article could be fused by an oxy-acetylene torch or the like but this was tedious and time-consuming and could not produce a transparent product.

Hot pressing was not used extensively in the commercial fabrication of fused silica products because of the inability to handle complex shapes and the requirement of specialized equipment, but it did permit higher densities than could be obtained by the usual slip casting methods. Experiments have been reported wherein fused silica powders were hot pressed at temperatures of 2000 to 2200F. using pressures of 1000 to 2500 pounds per square inch to produce a very high density. While such high pressure process might be suitable for producing flat glass plates or discs, it has not been used extensively and is not practical for producing the glass shapes usually desired.

For many years prior to the present invention, it was thought that glass working was the only practical methods for producing precision transparent amorphous quartz glass products, excluding those fairly simple shapes which can be cast without a mold in a resistance or arc-furnace as hereinafter described. For this reason, such transparent quartz glass products made during the last decade have been expensive. Those in the glass industry thought, prior to this invention, that less expensive methods, such as slip casting, could not produce transparent quartz glass products with a quality comparable to that of products made by glass working.

While this problem has existed for many years prior to the present invention, a satisfactory solution was not found. The problem was a difiicult one because of the nature of fused quartz and the need to avoid devitrification and the formation of substantial amounts of cristobalite. The latter undergoes the alpha-beta inversion at a temperature between 340 and 510F. and, when present in relatively small amounts, causes the fused quartz to crack when it reaches the inversion temperature during heating or cooling. Because the rate of formation of cristobalite increases rapidly when fused silica is heated above 2200F.*, it was thought prior to this invention that the firing temperatures for slip-cast products should be no higher than 2200F. This was considered important, particularly because the large exposed surface area of fused silica particles in the slipcast product which resulted in a higher devitrification rate. The 2200F. upper limit on firing temperatures was accompanied by an upper limit on density so that the utility of such slip-cast fused silica products made prior to this invention was limited.

(*The rate of formation of cristobalite at 2400F. is probably at least 10 times the rate of formation at 2200F.)

The need for a simple, inexpensive method of making transparent and/or high density amorphous quartz has existed for many decades. However, up to the time of the present invention, expensive glass working methods were considered the most practical for making quartz crucibles and most other precision amorphous quartz glass products. Some quartz glass products, such as bell jars, could be made by the less expensive arc-fusion process in which quartz sand is melted at a temperature above 3500F. while held in position against a graphite mold surface by centrifugal force. The unmelted sand separates the graphite mold surface from the melted silica to prevent reaction of the silica with the graphite. This process avoids substantial devitrification and makes it possible to produce an amorphous quartz glass with excellent resistance to thermal shock. However, the unmelted sand provides the resulting amorphous quartz glass product with a rough surface and poor dimensional accuracy which is unacceptable for most quartz glass products.

Where a precision high-denity fused silica product of high strength was required, as in the case of crucibles used to hold molten silicon, it was thought, prior to this invention, that expensive glass working was the-most practical way to meet the desired specifications.

In the case of the quartz crucibles, which were used to hold molten silicon during the growing of a silicon crystal rod, the product was considered unsatisfactory if it contained significant amounts of cristobalite or was misshapen. Such silicon crystal rods, which are cut to form wafers for use in microelectronic circuits, are made by melting the silicon metal in the quartz glass crucible by heating for about one-half hour to a drawing temperature of about 2585F., introducing a seed crystal, and pulling the crystal for a period of about 8 to 16 hours at such temperature. Even a transparent amorphous quartz glass crucible which is essentially free of cristobalite deteriorates and becomes brittle during this operation by devitrification, losing its transparency because of the formation of substantial amounts of cristobalite. The presence of even a relatively small amount of impurities or a small amount of cristobalite in the crucible at the beginning of the heating period can be unacceptable because it accelerates this deterioration, and, therefore, it was considered essential, prior to this invention, to employ transparent quartz glass crucibles of the highest quality preferably, pure quartz glass crucibles made by glass working, for example, from quartz glass tubing. Although such quartz glass crucibles were expensive, it was thought that there was no satisfactory substitute.

In recent years attempts have been made to make a less expensive product by sintering a slip-cast crucible but the results have not been completely satisfactory and do not approach the results obtained by the present invention. For example, the process of US. Pat. No. 3,6l9,440 is not practical for commercial production. The process of US. Pat. No. 3,620,702 is practical and is apparently used commercially but cannot produce a transparent product with a quality comparable to the more expensive glass-worked crucible and cannot maintain close tolerances because of the inherent nature of the torching process.

Applicants have discovered a simple unique process which will produce from powdered fused quartz a transparent amorphous quartz crucible of high density having the required strength, crack resistance, and resistance to devitrification and will avoid formation of significant amounts of cristobalite. The cost of manufacture of such transparent amorphous quartz crucibles is perhaps less than half that of the crucibles formed by glass working. Applicants process facilitates economical mass production, from the powdered fused quartz, of precision transparent glass crucibles having excellent resistance to thermal shock and having a quality comparable to that obtainable by glass working. For example, such crucibles having a temperature of 2700F. can be cooled without cracking by placing them in water at room temperature.

Applicants have discovered that high density fused quartz crucibles and otherprecision fused silica products of high quality can be made in a simple inexpensive manner from particles of essentially pure fused quartz or fused silica which are molded or formed by powder metallurgy techniques, such as slip casting or pressing. A slip-cast crucible, for example, which has been dried and fired at a high temperature, such as 2'100F., is heated rapidly to a high temperature, such as in the range of 3000 to 3100F., and maintained at a temperature in that range in a furnace for a short period of time, such as l to 5 minutes, to sinter the fused silica and to increase the density to 99 percent or greater while avoiding significant devitrification and maintaining the desired shape. Such heating may, for example, be carried out in a graphite-lined furnace containing an inert gas, such as helium, nitrogen or argon. Where the fused quartz article must be transparent it is possible to carry out the sintering in a vacuum, but the preferred method employs an atmosphere of helium. When using helium, the equipment required is very simple and a mass production process can be carried out at atmospheric pressure. The slip casting can also be carried out at atmospheric pressure with the simplest equipment.

It has been discovered that, in order to obtain a transparent amorphous quartz glass product with a quality approaching that of a glass-worked article, the slip-cast article must have a high purity and must be vacuum dried to remove essentially all of the water. The finished product should have an infrared absorption beta OI-I factor below 0.04 and preferably below 0.01 at a wavelength of approximately 3.5 microns, as measured on an infrared spectrophotometer. This may be achieved by firing or sintering the slip-cast or pressed crucible in a vacuum furnace at a suitable temperature,

such as 2000 to 2200F.. before the final heating in the induction furnace.

The apparatus of the present invention used in the manufacture of precision crucibles employs a shaped support or a mandrel which is formed of a refractory material, such as graphite. and which has a shape to conform to the surface of the crucible. Such support is at all times maintained at a high temperature, such as 2500F. or above, and is mounted to move quickly from an exposed loading position to a heating position within the furnace, wherein the crucible is heated to the desired sintering temperature.

In the preferred embodiment of the invention, the shaped support is a convex graphite susceptor and is mounted on a carriage within a separate cooling unit having refractory enclosing walls which move in unison with the carriage. Such cooling unit can be moved from a first loading position, at one side of the furnace, to a second position in alignment with the furnace chamber in which the graphite susceptor may be advanced into the furnace. The furnace is designed to heat the exterior surface of the crucible to a temperature above the interior surface so that trapped gas flows radially outwardly.

An object of the invention is to reduce the cost of manufacture of precision crucibles for the drawing of silicon crystal rods.

Another object of the invention is to provide a method and apparatus for avoiding substantial devitrification in the manufacture of sintered fused quartz crucibles.

A further object of the invention is to mass produce precision transparent amorphous quartz crucibles and other articles of extreme high quality at minimum cost.

Another object of the invention is to provide a simple mass production process and apparatus for increasing the density or a fused silica product and converting it from an opaque or translucent state to a transparent amorphous state while avoiding formation of significant amounts of cristobalite and maintaining the desired size and shape.

Another object is to provide a mass production process for making precision transparent quartz glass products at atmospheric pressure using simple equipment.

These and other objects, uses and advantages of the invention will become apparent to those skilled in the art from the following description and claims.

In the drawings:

FIG. 1 is a side elevational view of the apparatus of this invention on a reduced scale with parts omitted and parts broken away and shown in section, the moved position of the movable cooling unit being shown in dot-dash lines;

FIG. 2 is a transverse sectional view of the apparatus of FIG. 1 on a larger scale, the graphite susceptor and crucible being shown in the uppermost position;

FIG. 3 is a fragmentary perspective view with parts omitted showing portions of the frame, the refractory cover plate being shown in its normal position before it is swung in the direction of the arrow to cover the circular furnace opening;

FIG. 4 is a fragmentary perspective view with parts broken away and parts omitted showing the position of the parts just before removal of the finished crucible; and

FIG. 5 is a schematic electrical diagram illustrating one form of automatic control system.

The particles of fused silica used in the practice of the present invention should be essentially pure or have a purity of 99.95 percent or higher and preferably has a purity of at least 99.99 percent. The fused silica is considered essentially pure if it will contain no more than 0.05 percent of impurities when heated to a sintering temperature, such as 2200F. or higher. A somewhat lower purity might be tolerated if the impurity is a compound, such as silicon carbide, silicon nitride, zirconium oxide or aluminum oxide. Significant amounts of fluxing impurities should, of course, be avoided. The fused silica may contain a small percentage (e.g., less than one percent) of an organic material, such as polyurethane rubber, which burns off without leaving a substantial residue. Satisfactory results can, therefore, be obtained by grinding fused silica sand in a ball mill even if the resulting fused silica powder contains small amounts of rubber or other organic polymer.

The fused silica used in the practice of this invention is preferably a fused quartz of high purity obtained from quartz sand or rock crystal and may, for example, be obtained in the desired particle size by pulverizing' or grinding essentially pure fused quartz sand or rock crystal having a purity of 99.95 to 99.99 percent or higher. The fused quartz should be substantially free of foreign matter or should be cleaned so that, after grinding, the fused quartz has the necessary purity. Excellent results can also be obtained from synthetically produced fused silica having the necessary purity. In general, the results improve as the purity of the fused quartz increases. It is, therefore, preferable to maintain a purity of at least 99.97 percent.

The fused quartz may be pulverized in various ways without introducing significant amounts of impurities. This is preferably accomplished in a ball mill, but the fused quartz may also be pulverized by crushing or by explosion or impact of particles on each other at high velocity. Pulverization could be accomplished using a vibro-energy mill, a Katy mill, a rod mill or an ultrasonic mill, for example.

Excellent results can be obtained by grinding fused quartz (e.g., fused quartz sand) in a conventional ball mill having balls or stones formed of essentially pure quartz glass or fused silica and having a low ash rubber lining, such as a polyurethane rubber or other suitable organic lining. The liquid employed during gringing is preferably distilled water so that a slurry is produced suitable for conventional slip casting. However, the vehicle used for the slurry may be a liquid other than water, particularly a liquid which will evaporate without leaving a significant residue. A polar liquid, such as kerosene, for example, could be used, but best results are obtained when the vehicle is water.

The fused silica particles used in the practice of this invention should have a particle size no greater than 200 microns and preferably have a particle size not in excess of 100 microns. When slip casting is employed, the average particle size is between 1 and 70 microns and is preferably 2 to microns. The size of the fused silica particles should be suitable for slip casting as is well understood in the art. When making transparent amorphous quartz glass by the process of this invention, it is usually preferable to employ fused silica particles with an average particle size of l to 10 microns.

The materials used in the practice of this invention to form the crucible or other article consist essentially of fused silica particles and. where slip casting is employed, a suitable vehicle, such as distilled water. It is preferred not to employ additives or a binder to assist in holding the particles together, particularly when making a substantially transparent quartz glass.

The desired article may be formed from the pulverized fused quartz particles by a hotor cold-pressing operation or the like or by a conventional slip casting procedure using a porous mold with an interior surface shaped to conform to the exterior surface of the crucible or other desired article. The article can be slip cast at atmospheric pressure without application of additional pressure. The material used to form the porous mold may be plaster of Paris or other suitable mold material. If the mold material can contaminate the fused quartz, the mold should be coated or lined with a protective layer or graphite or other suitable material.

A mold release consisting essentially of graphite can be used to serve as a lubricant or parting agent and, if a plaster mold is used, to protect the fused silica from the plaster. The graphite may be brushed onto the mold surface to provide a thin protective coating, for example, with a thickness of a few microns. Such graphite should be substantially free of impurities or undesirable foreign matter and is preferably essentially pure.

AFter the porous mold has been coated with the graphite powder, the slurry containing pulverized fused silica suspended in distilled water is poured into the mold. The porous mold draws the water out of the slurry so that after a suitable period of time, such as 10 to 20 minutes or so, the desired wall thickness will be obtained. The time may be reduced somewhat by applying pressure to the slip, but it is preferable not to apply such pressure. At the end of such period, the mold is turned upside down to remove the excess slurry, returned to its upright position, and thereafter allowed to dry. The resulting slip-cast crucible will shrink slightly so that it can easily be removed from the mold. Such removal can be facilitated by directing air from a nozzle into the space between the crucible and the mold to blow off the crucible. At this stage the crucible has sufficient strength to support itself and can be dried in the conventional manner with or without internal support from a mandrel or the like.

After removal from the mold, the crucible or other casting should be dried thoroughly before firing to avoid damage from too rapid moisture evolution. Drying can be effected in various ways. A convenient method is to dry the casting overnight at 1 10 to F. and thereafter dry it for several more hours at a temperature of 300 to 400 1 If a mold release other than graphite is used, it may be necessary to clean the casting before firing. If any excess graphite is present on the casting, it can be removed before firing, but this may not be important as oxidation of the graphite during firing is usually effective and apparently does not have a substantial effect on devitrification.

The casting is preferably fired in air or steam or in an inert atmosphere prior to the final sintering or glassifying operation to eliminate combustibles, such as rubber particles from the ball mill lining. Such optional firing also eliminates any absorbed water which is not removed during the previous drying.

In a typical process, the casting may be thoroughly dried at a temperature of 100 to 400F. and then fired at a temperature of 2000 to 2200F. for a suitable period of time, such as 20 to 60 minutes or more, sufficient to eliminate the combustibles and to effect adequate sintering to strengthen the casting for easy handling. The casting would be maintained in a dry place until the final sintering treatment at a higher temperature (e.g., above 3000F.).

In the optional firing described above, the temperature is preferably not in excess of 2200F. so that cristobalite formation is minimized. Because it is not necessary to obtain a high strength during this firing, the sintering time for most castings can be limited to l or 2 hours to minimize cost and avoid unnecessary devitrification.

It has been discovered that normal firing of the slipcast crucible at atmospheric pressure does not provide the final amorphous glass product with the best quality and that vacuum drying is essential to assure top quality. The vacuum drying can be effected in various ways with varying degrees of vacuum (for example, at pressures of 1 to 100 torrs) and is preferably carried out at a pressure not in excess of 20 torrs and a temperature not in excess of 2200F.

The preferred procedure is to fire or sinter the slipcast or pressed crucible or other fused silica article in a vacuum furnace at a pressure of 0.5 to 10 torrs and at a high temperature, such as 2000 to 2200F., so that essentially all of the water is removed including the water of hydration on the silica particles. The amount of vacuum applied should be such that the amorphous quartz glass of the finished crucible or other article has an infrared absorption beta OH factor, as measured on an infrared spectrophotometer, that is below 0.04 and preferably below 0.01 at a wavelength of approximately 3.5 microns (for example, from about 0.001 to about 0.006). The vacuum drying as described above makes it possible to produce a transparent glass with high viscosity and high resistance to devitrification approaching that of quartz glass produced by glass working. It would be impossible to achieve such high quality using a crude process of the type disclosed in US. Pat. No. 3,620,702, for example.

After firing at 2100 to 2200F., the crucibles are usually cooled to room temperature. Because the fused silica casting has good thermal shock resistance, it may be heated very rapidly to the firing temperature by placing it in a preheated furnace or on a preheated graphite mandrel similar to the mandrel 16 shown herein. It may also be cooled rapidly in air after firing.

The dried slip-cast crucible or other casting produced in the manner described above is subjected to a final heating to effect vitrification at a temperature in the range of 3000 to 3l50F. without changing the shape of the article. This heating must be carried out in such a way as to avoid blistering or substantial devitrification and, therefore, the casting must be heated rapidly to a sintering temperature in the proper range (e.g., 3000 to 3l50F.) and held at that temperature for a limited period of time, such as l to 5 minutes, to obtain the desired precision fused quartz product. The casting cannot be allowed to remain at a temperature above 2200F. for too long a period of time because of devitrification.

ln the practice of this invention, the slip-cast fused silica crucible or other casting is heated rapidly, preferably by placing it on a hot mandrel or support, which has a temperature of 2500 to 3000F. and preferably 2600 to 2700F., and quickly moving the casting on the support into a furnace having a temperature above 3000F. (e.g., 3000 to 3200F.). The temperature of the crucible or other casting is rapidly raised from below 2200F. to 3000F. or higher in two minutes or less and preferably in one minute or less and is held in the range of 3000 to 3 l 50F. for a sintering period of l to 6 minutes to provide a density of at least 99 percent and preferably to provide a transparent or substantially transparent quartz glass. The heating is car ried out in a manner to maintain the desired size and shape and to provide a precision product. When making precision crucibles. said sintering period should be no more than 5 minutes and preferably about 2 to 4 minutes.

The crucible is cooled after the glass reaches the desired maximum temperature. which is usually 3050F. to 3100F. and preferably no more than 3 150F. When making relatively thick quartz glass articles, the sintering time may be somewhat greater and the maximum glass temperature at the surface may be as high as 3200F. before the article is cooled.

The quartz glass crucible is preferably removed from the furnace and cooled for a short period of time (i.e., one minute or less) on the graphite mandrel or form to an intermediate temperature, such as 2500 to 2700F. before the crucible is removed from the mandrel and cooled to room temperature. The crucible should be cooled to a temperature below 2200F. within 2 or 3 minutes after it is removed from the furnace and before there is significant devitrification.

In order to minimize formation of cristobalite, the crucible is heated to increase the temperature from 2200F. or below to the desired maximum glass temperature in no more than 8 minutes and is then cooled to a temperature below 2200F. so that the fused quartz is subjected to a temperature above 2200F. during such heating and cooling for a period of no more than about 10 minutes.

Highest quality fused silica products are produced by the process of this invention when the final sintering operation is carried out in a helium atmosphere or in a vacuum. Operation at atmospheric pressure with helium is preferred and makes possible mass production of precision transparent quartz glass articles at a fraction of the usual cost using relatively inexpensive equipment, for example, as described below. The process is also very reliable so that waste due to scrapping of defective pieces is minimized. The quality of the transparent product which can be consistently produced by mass production is admirable. The product has exceptionally good thermal shock resistance as can be readily demonstrated. For example, typical mass produced transparent quartz glass crucibles made by the process of this invention and having a temperature of 2000F. will not crack when placed in water at room temperature (i.e., F.) to effect immediate cooling. If desired, such drastic cooling may be employed to test the quality of the glass and to demonstrate the absence of significant amount of cristobalite.

Referring more particularly to the drawings, in which like parts are identified by the same numerals throughout the several views, FIGS. 1 and 2 show a special induction furnace constructed to perform the process of the present invention and having a stationary upper furnace unit A, a lower movable cooling unit B, and a rigid metal frame F for supporting the units A and B for providing a guide means for supporting the movable cooling unit and allowing it to be moved from the normal position shown in solid lines in FIGS. 1 and 2 to the unloading position shown in FIG. 4 and in dot-dash lines in FIG. 1.

The induction furnace unit A has an annular refractory body 1 which comprises a relative thick upper cylindrical portion 2, a cylindrical portion 3 of reduced thickness, and a helical copper heating coil 4 embedded in the refractory material of the body 1 coaxial with the internal cylindrical surface of said body 1. The top of the furnace unit A is covered by a flat circular refractory cap 5 which fits the body 1 in sealing engagement throughout its periphery. A flat circular refractory plate 63 of uniform thickness engages the flat bottom surface of the cap 5. A cylindrical refractory sleeve 6 of uniform thickness fits inside the body 1, as shown in FIG. 2, and extends from the margin of the plate 63 to a point near the bottom of the body 1. A flat plate 24 is provided under the body 1 and has a circular opening 26 with a diameter equal to the internal diameter of said body. A refractory plate 124 covers the plate 24 and engages the bottom of the body 1.

A cylindrical refractory heat sink or cup 7 of uniform wall thickness forms the cooling chamber 18 of the movable unit B and is positioned coaxial with the sleeve 6 and the furnace body 1 as shown in FIGS. 1 and 2. The flat annular upper surface of the cylindrical wall 8 of said cup is located adjacent to or closely spaced from the flat bottom surface of the plate 24 to retain gases in the chamber 18 with limited air flow through the small clearance space between the upper furnace unit A and the lower cooling unit B. Such clearance space is provided between the cup 7 and the plate 24 to permit easy movement of the unit B in a horizontal direction, but it will be understood that the vertical width of such space may be relatively small (for example, 0.03 to 0.1 inch).

The cylindrical refractory wall portion 8 is preferably integral with the flat circular base portion 9 and is surrounded by a helical copper cooling coil 10, which is coaxial with the cup. If desired, such coil can be embedded in the cup like the coil 4 described above. The water or other cooling fluid is constantly circulated through the coil 10 to maintain the walls 8 at a moderate temperature, such as 300 to 400F., and to effect cooling of the mandrel 16 at the desired rate. The base portion 9 has a central cylindrical hole 48 for receiving the piston rod 12, which remains coaxial with the wall 8 during reciprocation of the circular refractory support plate 11. The unit B shown herein has a doubleacting pneumatic cylinder 13 with a piston which reciprocates the support plate 11 between a normal retracted position in engagement with the base 9, as shown in FIG. 1, and an uppermost position adjacent to the bottom marginal surface of the sleeve 6, as shown in FIG. 2. The cylinder 13 may be rigidly mounted on the frame f of the unit B by means of a horizontal mounting plate 14 and bolts 15 as described in more detail hereinafter.

The support plate 11 shown herein is recessed to receive a circular plate 31 of uniform thickness having a flat upper surface perpendicular to the piston rod 12.

The lower surface of the support plate may be recessed in a similar manner to receive a flat circular metal plate 69 which is rigidly and detachably connected to the piston rod.

As herein shown, the refractory support plate 11 has a diameter slightly greater than the internal diameter of the sleeve 6 and less than the internal diameter of the circular hole in plates 24 and 124 so that the furnace chamber 37 is substantially closed when the plate 11 is in its upper position. However, a clearance space or other opening may be provided to allow some of the furnace gases to move downwardly through or past the plate 11. A continuous flow of helium may be provided through the furnace to flush out any air that may leak into the furnace during the cycle.

A shaped support or susceptor 16 of circular cross section is rigidly mounted on the flat upper surface of the refractory plate 31 in a position coaxial with the piston rod 12 so as to be located coaxial with the refractory sleeve 6 when a crucible c is placed in the furnace chamber 37 of the furnace unit A. The susceptor is preferably convex and has an exterior surface which is preferably smooth and which has a shape corresponding to the shape of the crucible. As herein shown, the susceptor comprises a mandrel having a hollow hemispherical upper portion 17, but it will be understood that the shape can vary substantially.

The material'used to form the furnace body 1, the cover 5, the cup 7 and the circular support plate 11 is preferably a ceramic or refractory material which is not damaged by high temperatures. Such material may be a conventional ceramic material used for metal casting and containing zirconium silicate, aluminum silicate, fused silica and/or refractory oxides, such as oxides of aluminum, zirconium, magnesium, beryllium or titanium. The inner surface of the furnace, the outer surface of the mandrel 16, and preferably also the inner surface of the cup 7 are formed of a refractory material, such as graphite or platinum, which is capable of withstanding temperatures of 3000 to 3400F. or higher, and which does not cause a damaging reaction with the fused quartz of the crucible. In the apparatus shown herein, the mandrel 16, the entire cup 7 of the cooling unit B, and the sleeve 6 and plates 31, 63 and 124 of the furnace A are formed of graphite. The latter material is usually preferred because of cost considerations but other materials can be used. Also the surface of the graphite may be covered with another material, such as platinum. The entire mandrel 16 can be made of platinum and provided with a smooth outer surface for engaging the glass crucible, but it is usually preferable to employ a less expensive refractory, such as graphite.

When induction heating is employed, the sleeve 6 should contain a material having magnetic susceptibility which can be heated by the induction coils of the furnace. The term susceptor is used herein to indicate such susceptibility. In the apparatus shown in the drawings, the convex form or mandrel 16, the plate 63, and the sleeve 6 are susceptors and function to heat the quartz crucible to the desired sintering temperature. The sleeve 6 and the plate 63 may be heated to a temperature of 3000F. to 3200F. or somewhat higher. The mandrel is heated to a lower temperature, such as 2950F to 3150F., during the sintering operation and is then cooled to a lower temperature, such as 2500 to 2700F. to facilitate handling of the crucible. After such cooling, the mandrel can be reheated before loading the next slip-cast crucible to a high temperature, such as 3000F., so that the crucible is heated as quickly as possible; but it is usually preferable to omit the extra heating step and to mount the next crucible on the mandrel when the mandrel is still at the lower temperature, such as 2700F.

It is preferable to provide a refractory cover plate or the like for covering the bottom end of the furnace body 1 when the unit B is moved away from the unit A. As herein shown, a flat circular cover plate 55 is provided for this purpose and is mounted to swing about pivot pins 61 into and out of a closing position. The refractory material used to form the cover plate 55 may be graphite and/or may be the same ceramic material used to form the furnace body 1.

As herein shown, the apparatus of this invention has a rigid metal frame F which includes a number of metal angles bolted, welded or otherwise rigidly connected together. The frame includes four vertical legs 19 that are interconnected at their upper ends by four horizontal angles 20 forming a rectangular horizontal framework. The legs 19 are rigidly connected to an intermediate rectangular framework comprising four horizontal metal angles 21, which support a rectangular flat plate or insulating board 23 in a horizontal position. Such board may be formed of a heat resistant material, such as asbestos or a pressed asbestos-like material, such as transite board, and may have a thickness of A to k inch. A similar insulating board 124 is supported in a horizontal position parallel to the board 23 by four metal angles 22. Circular holes 25 and 26 are provided at the centers of the insulating boards 23 and 124. respectively, as shown in FIG. 2 so that the furnace body 1 may be mounted with its axis in a vertical position and supported by the two insulating boards. A graphite plate 24 of the same shape as the board 124 and having a thickness of A and /2 inch may be mounted below said board. The frame F also includes a pair of horizontal longitudinal angles 27, which are rigidly connected to the bottom portion of the legs 19, and a pair of horizontal longitudinal angles 29 parallel to the angles 27. Short vertical angles 28 are rigidly connected between the angles 27 and 29 to provide supports for the horizontal angles 29 and for a pair of straight longitudinal rails 30, which are rigidly mounted on the angles 29. The rails engage the wheels 44 of the cooling unit B and provide means for guiding the unit horizontally from a normal operating position below the furnace unit A, as shown in solid lines in FIG. 1, to an unloading position below the insulating unit D, as shown in dot-dash lines in FIG. 1.

As herein shown, the unit D is rigidly mounted in cantilever fashion on the legs 19 of the frame F (see FIGS. 1 and 4). This unit comprises a pair of flat rectangular graphite plates 32 and 33 which are supported in horizontal positions on four metal angles 132 are spaced apart by four graphite bars 133 of square cross section which extend around the periphery of the unit D to seal the periphery of the narrow rectangular plenum chamber 35 formed within the unit I).

The graphite plates 32 and 33 are of the same size and shape and are provided with central openings having circular edge surfaces 36 with a diameter equal to or slightly greater than the external diameter of the crucible c, so that the crucible may be moved upwardly by the piston rod 12 through the unit D to the unloading position shown in FIG. 4. An inert gas, such as helium, is continuously fed into opposite sides of the plenum chamber 35 through flexible hoses 77 from helium tanks or other source of gas so that the hollow graphite susceptor 16 and/or the crucible c is bathed in the inert gas and maintained under non-oxidizing conditions when in the elevated position shown in FIG. 4. This prevents oxidation of the hot graphite of the susceptor 16 at an excessively high rate and provides the graphite susceptor with a useful life at least ID or 20 times that which would result if the unit D were omitted. This arrangement also facilitates cooling of the outer surface of the finished crucible c at the end of the cycle so that such surface is less likely to be deformed or damaged by the lifting tongs when it is raised off the graphite susceptor at the end of the cycle. A suitable inlet connection 76 may be provided on the associated graphite bar 133 for each of the hoses 77.

While non-oxidizing conditions are needed in the furnace A and the unit D to avoid oxidation of the graphite, such is not the case if the mandrel and the furnace plates are made of platinum instead of graphite.

The movable cooling unit B shown herein is in the form of a truck or carriage and has its own rigid metal frame f comprising a number of metal angles welded or otherwise rigidly connected together. The frame f includes four vertical legs 38, which are connected at their upper ends to a pair of longitudinal horizontal angles 39, and a pair of lateral horizontal angles 40, the angles 39 and 40 forming a rectangular framework for supporting a flat rectangular plate or insulating board 41 in a horizontal position parallel to the rails 30 and the insulating boards 23 and 124 described above. The plate 41 preferably comprises transite board. The lower ends of the legs 38 are rigidly connected to a pair of longitudinal horizontal angles 42 and a pair of horizontal lateral angles 43. Four grooved wheels 44 are pro vided on the frame f with their horizontal shafts 45 mounted on the angles 42. Each wheel has a central groove 46 of a size to receive the rail 30, as shown in FIG. 2, so that the unit B is accurately located as it is guided by the rails 30 during its reciprocations. Fixed stops 66 and 67 may be provided on the rails 30 to limit the travel and assist in locating the cup 7 in alignment with the furnace opening and the circular openings 36 of the unit D. Movement of the unit B between said stops may be effected manually in response to a signal or automatically by means of a suitable motor, such as the motor M of FIG. 1, and a suitable electrical control as shown in FIG. 5.

The air cylinder 13 and piston rod 12 may be mounted on the unit B in any suitable manner. As herein shown, the piston rod 12 extends through a small circular hole 53 in the mounting plate 14 and through similar holes 47 and 48 in the board 41 and the refractory base 9, respectively. As herein shown, means are provided for adjustably mounting the plate 14 on the longitudinal angles 42 including the threaded bolts 15 and the adjusting nuts 49 and 50.

As shown in FIGS. 1 and 3, the refractory cover plate is rigidly mounted on a circular metal hub 56 located on the upper end of a vertical support rod 57. Swinging means are provided for supporting the rod 57 including a horizontal supporting arm 58 having integral vertical sleeves S9 and at its opposite ends. The rod 57 fits snugly in the sleeve 59 and may be adjustably supported in any desired position. A vertical pivot pin 61 extends through the sleeve 60 and into the flanges of a U-shaped mounting bracket 62, which is rigidly mounted on one of the vertical legs 19. The pivot pin supports the arm 58 in a horizontal position and permits it to be swung from a normal retracted position, as shown in solid lines in FIGS. 1 and 3, to a closed position wherein the rod 57 is coaxial with the furnace body 1 and the cover plate 55 covers the bottom circular opening 26 of the board 24. The diameter of said cover plate is preferably equal to or greater than the internal diameter of the hole 26 and is so mounted that it will substantially close the bottom opening of the furnace chamber 37 when swung to said closed position.

It will be noted that the bottom surface of the board 24 is horizontal and below the angles 22 so that only the leges l9 obstruct movement parallel to that surface. Therefore, the flat upper surface of the cover plate 55 may be located at or spaced a very short distance below the lower surface of the board 24 and may be swung in that plane. Likewise, the upper surface of the refractory cup 7 may be located at or very near the board 24 without interfering with the reciprocating movement of the unit B.

In carrying out the process of the present invention, it is preferable to fill the furnace chamber 37 with helium and to maintain the helium atmosphere during the heating step. When employing helium in this manner, it is preferable to maintain a flow of helium into the furnace chamber at a slow rate sufficient to maintain the desired inert atmosphere and insufficient to interfere with proper heating of the furnace chamber.

As herein shown, an externally cylindrical block 70 formed of metal or a refractory material is rigidly mounted on top of the refractory cover 5. The block has a central vertical passage 151, which is aligned with the central vertical passage 51 of the cover 5 and the central hole 54 of the graphite plate 63 and has an inclined radial passage 72 extending from an inlet 73 to the passage 151. A quartz lens or sight glass 71 is mounted in a recess at the top of the passage 51 to permit viewing of the furnace chamber and use of a conventional optical pyrometer to measure the furnace temperature.

A flexible supply hose 74 is connected to the inlet 73 to supply helium to the furnace through the passages 72 and 51. Such hose is connected to a suitable constant pressure source of helium, such as one or more helium tanks having a constant pressure valve. The hoses 77 of the unit D may be connected to the same source.

It will be understood that the apparatus shown herein for purposes of illustration may be modified or improved in many ways and that various other means can be employed in the practice of this invention. Conventional temperature controls may, for example, be employed to maintain the desired temperature in the furnace in response to the temperature of the crucible or the furnace. Such controls may incorporate a pyrometer, such as a radiation or optical pyrometer, or other suitable means to measure the furnace temperature and/or the glass temperature.

FIG. 5 is a schematic electrical diagram illustrating one type of electrical control system which may be used to carry out the process of the present invention. The graphic symbols and basic device designations therein are generally in accordance with the electrical standards of the Joint Industrial Council as set forth for example in the April and May, 1967 issues of Electro- Technology." The lines of the control circuit are numbered 1 through 17 at the left of FIG. 5 and are referred to by these numbers in the description below.

In the electrical system illustrated there are four solenoids identified as 1 SOL through 4 SOL. The solenoid l SOL controls the supply of air to the double-acting pneumatic cylinder 13 and, when energized, causes the piston rod 12 to move upwardly and raise the graphite mandrel 16. The solenoid 2 SOL controls the supply of air to the opposite end of the pneumatic cylinder 13 and, when energized, causes the piston rod to move downwardly to lower the mandrel 16.

It will be apparent that various types of pneumatic cylinders, air motors or electric motors may be employed to effect reciprocation of the mandrel 16. The same is true in connection with reciprocation of the carriage at B. A motor M is shown schematically in FIG. 1 to represent a conventional means for reciprocating the carriage. Such motor may, for example, be a double-acting pneumatic cylinder similar to cylinder 13 or a reversible electric motor for effecting rotation of the wheels 44 to move the carriage from one stop 66 to the other stop 67.

The solenoid 3 SOL controls the motor M (FIG. 1) and, when energized causes the carriage B to move horizontally in a direction from the loading position to the operating position below the furnace A and against the stop 66. The solenoid 4 SOL also controls the motor M and, when energized, moves the carriage back toward the loading position below the unit D and against the stop 67. When the motor M is omitted, the solenoids 3 SOL and 4 SOL may be employed to operate a horn or ready light and thereby signal the operator that it is time to move the carriage so that the process may be carried out in the same manner.

The electrical system includes four normally-open limit switches lLS through 4LS which may be located in various positions to function in the desired manner. The limit switch lLS closes in response to movement of the mandrel 16 to its uppermost position, for example, in response to movement of the piston to the top of cylinder 13 (see FIG. 2). The switch 2LS closes in response to movement of the mandrel 16 to its lowermost position wherein the plate 11 is in engagement with the bottom of the cup 7. As herein shown, the limit switch 2LS has an actuator 68 which engages the bottom of the plate 11.

The limit switch 3LS closes in response to movement of the cooling unit B to the loading position shown in FIG. 4, wherein the carriage engages the stop 67. As shown in FIG. 4, the projection on the carriage at 39 engages the actuator 75 of the switch 3LS. The switch 4L3 closes in response to movement of the cool ing unit to the operating position below the furnace as shown in FIGS. 1 and 2, wherein the carriage engages the stop 66. When the cooling unit arrives at that position, it engages the actuator 64 of the switch 4LS to close the switch.

In the operation of the machine the cycle begins with the cooling unit B in the loading position of FIG. 4 and the mandrel 16 in the lowermost position. The operator starts the cycle by depressing the pushbutton FBI to close the circuit in lines 1 and 3. This energizes the main control relay 9CR, which is maintained energized by closing of its contacts in line 2, and also energizes the timer relay 2TR, which is maintained energized by closing of its contacts in line 4. The closing of the main relay contacts in line 2 results in energizing of the control relay 3CR, assuming that the cooling unit B is in its expected loading position to close the limit switch 3L8. The normally-open 3CR contacts close in line 4 to energize the solenoid l SOL and thereby raise the mandrel 16. When the mandrel its uppermost position, the limit switch lLS closes to energize the relay lCR and the normally closed ICR contacts in line 4 open to deenergize the solenoid I SOL.

The timer 2TR provides the operator with a predetermined time delay to place the slip-cast crucible c on the mandrel 16 as shown in FIG. 4. At the end of this time delay the normally-closed 2TR contacts open in line 4 and the normally-open 2TR contacts close in line 6 to energize the timer relay 3TR, which is maintained energized by closing of its contacts in line 7, and to energize the solenoid 2 SOL in line 10 and lower the mandrel 16 to its lowermost position. When it arrives at that position, the limit switch 2LS closes to energize the relay 2CR and open the normally-closed 2CR contacts in line 10, thereby deenergizing the solenoid 2 SOL. At the same time the normally-open ZCR contacts in line 8 close to energize the solenoid 3 S01 and cause the cooling unit B to move from the loading position of FIG. 4 to the operating position of FIG. 2. When the unit arrives at the operating position, the limit switch 4LS closes to energize the relay 4CR and to open the 4CR contacts in line 8, thereby deenergizing the solenoid 3 SOL. At the same time the normally-open 4CR contacts in line 5 close to energize the solenoid l SOL and raise the mandrel, the normally-open 3TR contacts in lines 5 and 7 being closed at this time. When the mandrel arrives at its uppermost position in the furnace, as shown in FIG. 2, the limit switch lLS closes to energize the control relay ICR and open its normallyclosed contacts in line 4, thereby deenergizing the solenoid l SOL.

The heating time in the furnace is controlled by the timer relay 3TR so that the crucible is heated to a temperature within the desired range (e.g., 3000 to 3100F.) for a predetermined period of time, such as l to 3 minutes. At the end of this time the normally-open 3TR contacts in line 11 close to energize the timer relay 4TR whose normally-open contacts in line 9 close immediately to energize the solenoid 2 SOL. This lowers the mandrel to its lowermost position in the cooling unit B, whereupon the limit switch 2L5 closes to energize the relay ZCR, open the normally-closed 2CR contacts in line 9 and close the normally-open 2CR contacts in line 12.

The timer relay 4TR provides a predetermined time delay, such as one-half minute or so, to allow the mandrel 16 and the crucible c to cool down to a temperature, such as 2700F., at which the glass of the crucible is sufficiently firm to permit gripping. This temperature is preferably about 2700F. but may be a few hundred degrees lower than this. A lower temperature such as 2400F. is undesirable in that is increases the time for each cycle and thereby favors the formation of cristobalite. The timer 3TR is, therefore, adjusted to complete the cycle before the crucible cools to such a low temperature (for example, to provide a time delay of 20 to 40 seconds).

At the end of the preselected cooling period, the relay 4TR closes its contacts in line 12 to energize the solenoid 4 S01 and thereby causes movement of the cooling unit B to the loading position below the unit D. When it arrives at that position (see FIG. 4). the limit switch 3L5 closes to energize the relay 3CR and closes its contacts in line 13, thereby energizing the relay SCR. The normally-closed SCR contacts then open momentarily in line 2 to deenergize the main control relay 9CR and terminate the cycle. The operator must. therefore, depress the pushbutton FBI to start another cycle to raise the mandrel to the uppermost position shown in FIG. 4. After the mandrel is in such position, he may remove the finished mandrel with conventional tongs and place another slip-cast crucible on the mandrel within the time permitted by the timer ZTR.

The cycle may be repeated rapidly to effect mass production of crucibles at a relatively high rate, such as 15 to 20 per hour, depending on the size of the crucibles and the temperatures employed.

It will be manifest that the electrical system may be made fully automatic so that the pushbutton PB] need not be depressed at the beginning of each cycle. However, when the apparatus is loaded and unloaded manually, a pushbutton of this type is usually preferred.

The simple furnace shown herein is adequate for crucibles commonly used at the present time and capable of heating the crucible to a temperature in the range of 2950 to 3 F. for the desired sintering period. However, more uniform heating is desirable for extremely large crucibles so that the heating time will depend less on the axial length of the crucible and more on the wall thickness. However, relatively short heating times can be employed even when the wall thickness is as high as 0.4 inch. The wall thickness of the crucible is usually no more than 0.3 inch even for large crucibles and is preferably no more than 0.2 inch.

It will be apparent that the refractory cover plate 55 may be moved by a pneumatic cylinder rather than by hand and that the electrical control system may include means to effect automatic opening and closing of the furnace opening by such plate, if this is desired.

It will be understood that the type of electrical system used to carry out the process of this invention may be of various types. No particular advantage is claimed for the type illustrated herein over other types which can be used. For example, the system could employ equipment of the general type shown in US. Pat. No. 3,356,130 (Mellen et a1.) and could employ conventional timing means and temperature control means of various types.

In carrying out the process of this invention, it is preferable to employ molded or slip-cast crucibles consisting essentially of fused silica that is, fused silica having a purity of at least 99.95 percent. A fused silica of the desired particle size may be obtained by milling, grinding or otherwise pulverizing fused quartz of high purity.

For example, fused quartz sand having a high purity, such as 99.97 to 99.99 percent, may be ground in a special ball mill without introducing significant contamination. Such ball mill may be a conventional ball mill having 1.5-inch diameter balls formed of pure fused quartz and a conventional rubber lining formed of a low-ash rubber such as polyurethane rubber or other organic material which will not cause significant permanent contamination. The example which follows is intended to illustrate the practice of the invention without limiting its scope.

Fused quartz sand with a purity of at least 99.97 percent is placed in the special ball mill described above together with distilled water and ground to minute size (325 mesh) to produce a conventional slurry suitable for subsequent slip casting. The average particle size is about 2 to 4 microns. Abbout four parts by weight of the fused quartz sand are employed for each part of water in each batch. A substantial number of batches are produced in this way, each having a weight of around 200 pounds.

Slip casting may, thereafter, be carried out using a conventional porous mold, such as a graphite mold or a graphite-lined plaster mold, having an internal surface with a shape corresponding to that of the external surface of the desired crucible (for example, the crucible of FIGS. 1 and 2). Before the slurry produced in the manner described in the previous paragraph is poured into the mold, the internal surface is wetted with water and coated with pure powdered graphite of small particle size, such as to 50 microns. The dry graphite powder is rubbed on the wet surface of the mold to provide a continuous shiny black coating, and any excess graphite is then wiped off.

The slurry is then poured into the mold and, after a suitable period, such as 10 to minutes, sufficient to obtain a wall thickness of about 0.1 inch, the mold is turned upside down to drain off the excess slurry and returned to the upright position. After drying for 30 minutes or so at 110F. until it has adequate strength to support itself, the resulting crucible is removed from the mold and dried for 4 hours at 1 10F. Such crucible may, for example, have a wall thickness of 0.1 inch, an axial length of five inches and an external diameter of 5 inches.

The partially dried crucible is then placed in a heating chamber having a temperature of about 350F. for a period of time at least sufficient to effect thorough drying (e.g., l to 4 hours) and the temperature of the air in the heating chamber is then raised slowly to a sintering temperature of 2lO0F. to eliminate combustibles, to eliminate any adsorbed water not previously removed, and to increase the strength of the crucible. After a sintering period, such as l to 2 hours, sufficient to provide strength for handling, the crucible is rapidly cooled with air to room temperature.

Dried slip-cast crucibles formed in this manner are then treated in equipment of the type shown in FIGS. 1 to 4 by placing each crucible on the graphite mandrel 16 when it is in the position shown in FIG. 4 and has a temperature of about 2700F. The crucible is automatically fed to the furnace chamber on the mandrel and heated in the helium atmosphere for a suitable period of time, such as 3 to 4 minutes, to a temperature of about 3050F. until the crucible is transparent. At the end of such period, the crucible is automatically lowered to the position shown in FIG. 1 and allowed to cool in the helium atmosphere for around one-half minute to a temperature of about 2700F. The crucible is then moved to the unloading position shown in FIG. 4 and removed manually by tongs or the like. It may be cooled rapidly to room temperature without breakage by placing it in water, but such rapid cooling is not necessary. The amount of cristobalite present is substantially less than one percent and obviously insignificant as evidenced by the transparency of the glass.

In carrying out the process described above, the sleeve 6, the plate 63, and other parts of the furnace may have a surface temperature of 3l00 to 3200F. The 'glass of the crucible is heated to 3050F. in the above example. While a higher maximum glass temperature, such as 3 150F. can be used, it is preferable to avoid the higher temperatures because of the tendency to produce surface blistering. High temperatures also hasten oxidation of the graphite parts and reaction of the silica with graphite to form carbon monoxide gas. Silicon monoxide gas is also formed due to reaction of graphite with silicon dioxide. The process of this invention is carried out in such a way as to minimize the damage done by trapped gases during sintering and to cause such trapped gases to move radially outwardly and thus not damage the internal surface of the crucible.

The transparent glass crucible of the above example is materially improved if the initial sintering at 2100F. is carried on in a vacuum furnace at a suitable low pressure, such as 10 torrs or less, to remove essentially all of the water so that the glass of the finished transparent crucible has an infrared absorpiton beta OH factor below 0.01 at a wavelength of 3.5 microns. Such glass has a much greater resistance to devitrification than a glass which would be produced by the procedure of the above example if firing were at atmospheric pressure.

In the practice of the present invention it will be understood that any fused silica can be used if it has the required high purity. As used in the present application, the broad term fused silica" covers various forms of vitreous silica including synthetic vitreous silica (for example, produced from silica resulting from conversion of a silicon compound), fused quartz produced from clear crystalline quartz, and vitreous silica produced from sand. The latter may be transparent, trans lucent or opaque. The process of this invention may,

for example, be employed to treat a crucible formed on a platinum or graphite mandrel by conversion of a silicon compound such as silicon chloride vapor.

The process of the present invention is well suited to the production of precision transparent quartz glass of very high quality in many different sizes and shapes, and it will be understood that many different methods may be employed to mold or form the article including slip casting, isostatic pressing, injection molding, hot pressing and the like, and that the shaping surface of the mold may be formed of or coated with many different materials which minimize contamination of the final product including carbon, graphite or high-purity combustible organic materials, such as polyurethane or Teflon, which can be eliminated by firing of the molded article, or silicon metal or silicon-containing compounds which are not objectionable in the final product, such as silicon carbide, silicon nitride (Si N.,) or silica (SiO For example, when the article is one which can be shaped by pressing at 10,000 to 50,000 pounds per square inch, the steel shaping surfaces can be coated with high-purity carbon, graphite, polyurethane or Teflon or with a high-purity material selected from the group consisting of silicon metal, silicon carbide, silicon nitride, silica and mixtures thereof. The shaping surface is preferably formed to the desired shape with close tolerances and with a very smooth surface preferably having pores no greater than 10 microns in diameter. The smooth shaping'surface is particularly important when making transparent quartz glass products because a rough surface on the finished article reduced transparency by interfering with light transmission and makes the glass look impure.

It will be understood that, unless the context shows otherwise, the term transparent, as used in the specification and claims in connection with the glass resulting from the process of this invention, refers to the glass itself regardless of the smoothness of the surface. It will also be understood that high quality molds can produce the desired surface so that the article itself as removed from the induction furnace is fully transparent without subsequent polishing While the process of the invention is particularly well suited to production of thin-walled articles, such as cru' cibles, evaporating dishes and glass tubing, it is also advantageous for the manufacture of large bell jars, and various other molded or slip-cast articles. The process may be used for the manufacture of beakers, flasks, heat shields, tapered joints, acid tanks, reactor vessels and various other articles, particularly quartz glass articles used in the chemical industry or the semiconductor industry.

Crucibles made according to the process of this invention contain substantially less than one percent cristobalite and usually have a thermal shock resistance such that they will not crack when plunged in water at 70F. while at a temperature of 2000F. This applies to the transparent or full density products and also to those with a density which is 99 percent of full density.

The size of the crucibles may vary considerably. Usually the crucibles have a wall thickness of about 0.08 to 0.15 inch, a diameter of 4 to 8 inches and an axial length of 4 to 8 inches. However, this invention makes it feasible to produce larger crucibles, for example, with somewhat thinner walls, diameters of 10 inches or so, and axial lengths of 10 inches or so.

It will be understood that, in accordance with the provisions of the patent laws, variations and modifications of the specific methods and devices disclosed herein may be made without departing from the spirit of the invention.

Having disclosed our invention, we claim:

1. A process for manufacturing precision amorphous silica glass articles from amorphous silica comprising at least 99.95 percent silica and having an average particle size no greater than 70 microns comprising forming, drying and firing a slip-cast article from said silica having a shape that is capable of being inside-supported during sintering, placing the dry rigid slip-cast article on a heated refractory support shaped to fit against the inner surface of said article, rapidly heating the article on said support from a temperature below 2200 F. to a sintering temperature of at least 3000 F., maintaining the temperature of the article from about 3000 F. to about 3150 F. in a vacuum or a helium atmosphere of a furnace for a period of at least several minutes to coalesce the particles while maintaining the original shape of the article, said period being such as to main tain the entire glass article in the amorphous state, said receptacle being sintered in said'furnace until the glass is transparent, cooling the resulting transparent amorphous silica glass article, and removing it from said support.

2. A process as defined in claim 1 wherein the furnace temperature is maintained higher than the temperature of the internal surface of said article during heating of the quartz article so that gas trapped in the article tends to move radially outwardly.

3. A process as defined in claim 2 wherein the quartz article is heated from a temperature below 2200F. to a temperature of at least 3000F. in less than one minute to minimize devitrification.

4. A process as defined in claim 3 wherein the article is maintained under a high vacuum at a sintering tem perature in said range until the article reaches full density.

5. A process as defined in claim 1 wherein an atmosphere of helium gas is provided in the furnace during heating of the quartz article and the article is maintained at a sintering temperature in said range until the article is substantially transparent.

6. A process as defined in claim 1 wherein the furnace temperature during heating of said quartz article is not in excess of 3200F.

7. A process according to claim I in which the maximum temperature of the transparent article during sintering in said furnace is no more than 3200 F. and in which the article is heated from below 2200 F. to said maximum temperature in no more than about 8 minutes.

8. A process for mass producing precision transparent amorphous silica glass receptacles comprising placing on a heated refractory support a dry rigid slip-cast receptacle formed of amorphous silica particles comprising at least 99.95 percent silica, said refractory support being shaped to fit and support the inner surface of said receptacle, rapidly heating said receptacle on said support from a temperature below 2200" F. to a sintering temperature in the range of about 2950 F. to about 3 F., maintaining the receptacle on said support at a temperature in said range in a furnace in a helium atmosphere or in a vacuum for a period up to about 6 minutes to coalesce the particles while maintaining the glass in the amorphous state, the heating being controlled to maintain the original shape of the receptacle as it approaches full density and to effect sintering until the glass is transparent, cooling the re sulting transparent amorphous silica glass receptacle, removing the glass receptacle from the refractory support, placing another slip-cast amorphous silica receptacle on said support, and repeating the process to form other transparent giass receptacles.

9. A process according to claim 8 in which the molded receptacle is placed on said refractory support while said support is at a temperature of about 2500 to 3000F. to effect rapid heating of the article and to im z sstitrift at rh 10. A process according to claim 8 in which the molded quartz receptacle is formed by slip casting and is thoroughly dried before being mounted on said re- FY QBB IP 11. A process according to claim 10 in which the receptacle is slip cast in a porous concave mold having an internal surface coated with graphite particles.

1 2: A tYocess according to claim 10in which said receptacle is a cup-shaped crucible with a wall thickness from about 0.1 to about 0.3 inch and said crucible is heated in said furnace to a sintering temperature within said range which is not in excess of about 3100F.

13. A process according to claifn8 in which the furnace temperature is maintained higher than the temperature of the internal surface of said receptacle during heating of the quartz article so that gas trapped in the walls of said receptacle tends to move radially out ward 14. A process according to claim 8 in which said refractory support is a graphite susceptor having a convex upper surface shaped to fit the inner surface of said receptacle and said molded receptacle is placed on said susceptor while the latter is at a temperature of about 2500 to 3000F. to effect rapid heating of the receptacle and to minimize devitr ification.

A mass production process according t'diim 8 16. A mass production process accordirigjtTcTaiin i5 in which said container has refractory enclosing walls at the bottom and sides and an opening at the top which may be aligned with the furnace opening at the bottom of the furnace to permit vertical movement of the graphite susceptor between said furnace and said container, and in which said container is moved horizontally to a loading position where said susceptor is lifted and exposed to permit removal of the transparent q a tz la ptacle-V a.

1 7. A mass production process according to ciaihi'i in which the molded fused quartz receptacle is place cf on the graphite susceptor at said loading position, said receptacle and said susceptor are lowered into said refractory container, said container is advanced to a positinn under the furnace in alignment with the furnace opening, said susceptor and said molded receptacle are raised into said furnace and held in the furnace for a predetermined period of time not in excess of six minutes, said susceptor and said receptacle are then lowered into said container and maintained in said cooling position for a predetermined period of time not in excess of one minute, and said container is then returned to said loading position.

13 A mass production process according to claim 17 in which the graphite susceptor is bathed in an inert gas during mounting and removal of the receptacle to minimize oxidation of the susceptor.

1?: A mass production process according to claim 8 in which each molded receptacle is formed by slip casting pulverized fused amorphous quartz cullet having an average particle size no greater than microns, said refractory support is a graphite mandrel, said mandrel is heated by induction in an induction furnace, and each receptacle is rapidly heated on said mandrel and in said furnace to form a transparent quartz glass receptacle with a peripheral wall thickness from about 0.08 to about 0.15 inch and having a shock resistance such that the article will not crack when submerged in water at F-1xhsa1hsahetemperatu e is .0 0?- 20. A process according to claim 8 in which said particles comprise amorphous silica having an average particle size not in excess of 70 microns.

211 A process according to claiiii fi in which said amorphous quartz glass receptacle is cooled to a temperature below 2700F. in a period of time not in excess of about one minute before being removed from said refractory support.

@3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,837,825 Dat d December 6. 1974 Inventofls) 'I'eg A. Loxlev et a1- It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 22, line 25, after "ZOOO F." insert the maximum temperature of the glass during such heating ,being no more than about 3200F-.

Signed and sealed this 29th day of April 1975.

(SEAL) Attest:

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

1. A process for manufacturing precision amorphous silica glass articles from amorphous silica comprising at least 99.95 percent silica and having an average particle size no greater than 70 microns comprising forming, drying and firing a slip-cast article from said silica having a shape that is capable of being insidesupported during sintering, placing the dry rigid slip-cast article on a heated refractory support shaped to fit against the inner surface of said article, rapidly heating the article on said support from a temperature below 2200* F. to a sintering temperature of at least 3000* F., maintaining the temperature of the article from about 3000* F. to about 3150* F. in a vacuum or a helium atmosphere of a furnace for a period of at least several minutes to coalesce the particles while maintaining the original shape of the article, said period being such as to maintain the entire glass article in the amorphous state, said receptacle being sintered in said furnace until the glass is transparent, cooling the resulting transparent amorphous silica glass article, and removing it from said support.
 2. A process as defined in claim 1 wherein the furnace temperature is maintained higher than the temperature of the internal surface of said article during heating of the quartz article so that gas trapped in the article tends to move radially outwardly.
 3. A process as defined in claim 2 wherein the quartz article is heated from a temperature below 2200*F. to a temperature of at least 3000*F. in less than one minute to minimize devitrification.
 4. A process as defined in claim 3 wherein the article is maintained under a high vacuum at a sintering temperature in said range until the article reaches full density.
 5. A process as defined in claim 1 wherein an atmosphere of helium gas is provided in the furnace during heating of the quartz article and the article is maintained at a sintering temperature in said range until the article is substantially transparent.
 6. A process as defined in claim 1 wherein the furnace temperature during heating of said quartz article is not in excess of 3200*F.
 7. A process according to claim 1 in which the maximum temperature of the transparent article during sintering in said furnace is no more than 3200* F. and in which the article is heated from below 2200* F. to said maximum temperature in no more than about 8 minutes.
 8. A process according to claim 1 in which, prior to sintering, the slip-cast article Is heated to a high temperature not in excess of 2200* F. under a high vacuum, such vacuum drying removing the surface water of hydration on the silica particles so that the finished transparent amorphous silica glass article has an infrared absorption beta OH factor as measured on an infrared spectrophotometer below 0.04 at a wave length of approximately 3.5 micron.
 9. A process for mass producing precision transparent amorphous silica glass receptacles comprising placing on a heated refractory support a dry rigid slip-cast receptacle formed of amorphous silica particles comprising at least 99.95 percent silica, said refractory support being shaped to fit and support the inner surface of said receptacle, rapidly heating said receptacle on said support from a temperature below 2200* F. to a sintering temperature in the range of about 2950* F. to about 3150* F., maintaining the receptacle on said support at a temperature in said range in a furnace in a helium atmosphere or in a vacuum for a period up to about 6 minutes to coalesce the particles while maintaining the glass in the amorphous state, the heating being controlled to maintain the original shape of the receptacle as it approaches full density and to effect sintering until the glass is transparent, cooling the resulting transparent amorphous silica glass receptacle, removing the glass receptacle from the refractory support, placing another slip-cast amorphous silica receptacle on said support, and repeating the process to form other transparent glass receptacles.
 10. A process according to claim 9 in which the molded receptacle is placed on said refractory support while said support is at a temperature of about 2500* to 3000*F. to effect rapid heating of the article and to minimize devitrification.
 11. A process according to claim 9 in which the molded quartz receptacle is formed by slip casting and is thoroughly dried before being mounted on said refractory support.
 12. A process according to claim 11 in which the receptacle is slip cast in a porous concave mold having an internal surface coated with graphite particles.
 13. A process according to claim 11 in which said receptacle is a cup-shaped crucible with a wall thickness from about 0.1 to about 0.3 inch and said crucible is heated in said furnace to a sintering temperature within said range which is not in excess of about 3100*F.
 14. A process according to claim 9 in which the furnace temperature is maintained higher than the temperature of the internal surface of said receptacle during heating of the quartz article so that gas trapped in the walls of said receptacle tends to move radially outward.
 15. A process according to claim 9 in which said refractory support is a graphite susceptor having a convex upper surface shaped to fit the inner surface of said receptacle and said molded receptacle is placed on said susceptor while the latter is at a temperature of about 2500* to 3000*F. to effect rapid heating of the receptacle and to minimize devitrification.
 16. A mass production process according to claim 9 in which said graphite susceptor is moved between a heating position within an induction furnace and a cooling position outside said furnace wherein the susceptor is enclosed in a container having a non-oxidizing atmosphere, the helium atmosphere of the furnace being maintained at a temperature above 3000*F. and above that of the graphite susceptor, whereby trapped gas in the quartz article will move radially outwardly away from the surface of said susceptor.
 17. A mass production process according to claim 16 in which said container has refractory enclosing walls at the bottom and sides and an opening at the top which may be aligned with the furnace opening at the bottom of the furnace to permit vertical movement of the graphite susceptor between said furnace and saiD container, and in which said container is moved horizontally to a loading position where said susceptor is lifted and exposed to permit removal of the transparent quartz glass receptacle.
 18. A mass production process according to claim 17 in which the molded fused quartz receptacle is placed on the graphite susceptor at said loading position, said receptacle and said susceptor are lowered into said refractory container, said container is advanced to a position under the furnace in alignment with the furnace opening, said susceptor and said molded receptacle are raised into said furnace and held in the furnace for a predetermined period of time not in excess of six minutes, said susceptor and said receptacle are then lowered into said container and maintained in said cooling position for a predetermined period of time not in excess of one minute, and said container is then returned to said loading position.
 19. A mass production process according to claim 18 in which the graphite susceptor is bathed in an inert gas during mounting and removal of the receptacle to minimize oxidation of the susceptor.
 20. A mass production process according to claim 9 in which each molded receptacle is formed by slip casting pulverized fused amorphous quartz cullet having an average particle size no greater than 70 microns, said refractory support is a graphite mandrel, said mandrel is heated by induction in an induction furnace, and each receptacle is rapidly heated on said mandrel and in said furnace to form a transparent quartz glass receptacle with a peripheral wall thickness from about 0.08 to about 0.15 inch and having a shock resistance such that the article will not crack when submerged in water at 70*F. when the glass temperature is 2000*F.
 21. A process according to claim 9 in which said particles comprise amorphous silica having an average particle size not in excess of 70 microns.
 22. A process according to claim 9 in which said amorphous quartz glass receptacle is cooled to a temperature below 2700*F. in a period of time not in excess of about one minute before being removed from said refractory support. 